Synthesis and Dynamic NMR Study of Functionalized 1-(3-Furyl)-1<Emphasis Type="Italic">H</Emphasis>-indole-2,3-diones

Summary. Protonation of the highly reactive 1:1 intermediates produced in the reaction between alkyl(aryl) isocyanides and dibenzoylacetylene by isatin, leads to vinylnitrilium cations, which undergo carbon-centered Michael-type addition with the conjugate base of the NH-acid to produce highly functionalized 1-(3-furyl)-1H-indole-2,3-diones. A dynamic NMR effect is observed in the ¹H NMR spectra of these compounds as a result of restricted rotation around the single bond linking the indole moiety and the furan system. The free-energy of activation (ΔG ^#) for this process is 69–71 ± 2 kJ mol⁻¹.     

Synthesis and Dynamic NMR Spectroscopic Study of Dialkyl 4-Ethoxy-1-(1-naphthyl)-5-oxo-4,5-dihydro-1 H-pyrrole-2,3-dicarboxylates

Protonation of the reactive 1:1 intermediate produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates with ethyl 2-(1-naphthylamino)-2-oxoacetate, leads to a vinylphosphonium salt, which undergoes intramolecular Wittig reaction to produce dialkyl 4-ethoxy-1-(1-naphthyl)-5-oxo-4,5-dihydro-1H-pyrrole-2,3-dicarboxylates in excellent yields. A dynamic NMR effect is observed in the ¹H NMR spectra of the title compounds as a result of restricted rotation around the single bond linking the naphthalene moiety and the heterocyclic system, which is attributed to the peri interaction between the pyrrole residue and the peri CH group. The free energy of activation (G ) for this process is 58±2kJmol^–1.     

Synthesis and in vitro-Anti-hepatitis B Virus Activities of Several Ethyl 5-Hydroxy-lH-indole-3-carboxylates

A series of ethyl 5-hydroxyindole-3-earboxylates 6a-10r was designed and synthesized. The structures of all the compounds were confirmed by IR, ^1H NMR, and MS and their anti-hepatitis B virus （HBV） activities were evaluated in 2.2.15 cells. Among them, compound 7g { ethyl 5-hydroxy-2- [ （ 3-methoxyphenylsulfinyl ） methyl ] -1-methyl-4- [ （4-methylpiperazin-1-yl） methyl ]-1H-indole-3-carboxylate} displays a significant anti-HBV activity, which is more potent than the positive control lamivudine.     

Convenient Synthesis of 3-(1-Carboxyalkyl)pyrido[2,3-d]pyrimidine-2,4-diones

A cheap and safe synthetic route to obtain 3-(1-carboxyalkyl)pyrido[2,3-d]pyrimidinediones (carboxyalkyl = -CHRCO₂H; R = H; CH₂; CH₂Ph; Ph; CH₂ (C₃H₃N₂); (CH₂)₂CO₂H; CH₂CO₂H) starting from 2,3-pyridinedicarboxylic acid is described. A process scheme consistent with empirical observations is proposed.     

New Synthesis of 3-(2-Furyl)phthalides

3-(2-Furyl)phthalides were synthesized for the first time by the reaction of 2-formylbenzoic acids with furan derivatives in the presence of an acidic catalyst. It was found that the reaction of 2-formylbenzoic acids and 2-alkylfurans in aqueous dioxane in the presence of perchloric acid leads to a mixture of 2-carboxyaryldifurylmethanes and 3-furylphthalides, which can be separated easily by preparative column chromatography. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1302–1304, September, 2005.     

Five-membered 2,3-dioxoheterocycles: LXXXIV. [4+2]-Cycloaddition of styrene to 4,5-diaroyl-1H-pyrrole-2,3-diones. Crystal and molecular structures of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethylphenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b]-pyrrole-2,3(1H,6H)-dione

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones react with styrene to form substituted 7,7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)-diones whose structure was confirmed by XRD analysis. The crystal and molecular structure of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethyl-phenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)dione was examined.     

Hypbrvalent Iodine Oxidation of 3-(2-Furyl)-1-(2-hydroxyaryl)prop-2-enones : Synthesis of Novel 2-(2-Furyl)-cis-3-hydroxvchromanones and Derived 3-Hydroxychromones

The synthesis of novel 2-(2-furyl)-cis-3-hydroxychro-manones(3a-c) has been achieved from 3-(2-furyl)-1-(2-hydroxy-aryl)-2-enones (1a-c) via acid catalyzed hydrolysis of dimethylacetals (2a-c), formed by hypervalent iodine oxidation using iodobenzene diacetate in methanolic potassium hydroxide. Action of dil. alkali on 3a and 3b provides a new synthesis of 2-(2-furyl)-3-hydroxychromones (6a, 6b).     

Five-Membered 2,3-Dioxo Heterocycles: LXXI.* Recyclization of 4,5-Diaroyl-1H-pyrrole-2,3-diones by the Action of Substituted Hydrazines. Crystalline and Molecular Structure of 2-(3-Benzoyl- 1-benzyl-5-phenyl-1H-pyrazol-4-yl)-N-(4-methoxyphenyl)- 2-oxoacetamide

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones reacted with benzyl- and phenylhydrazines to give N-aryl-2-(5-aryl-3-aroyl-1-benzyl(phenyl)-1H-pyrazol-4-yl)-2-oxoacetamides whose structure was proved by X-ray analysis.     

Synthesis, chemical properties, and antimicrobial activity of 2- and 2,3-substituted [(tetrahydro-2,4-dioxopyrimidin-1(2H)-yl)phenoxy]naphthalene-1,4-diones

Abstract  

Mono- and disubstituted [(tetrahydro-2,4-dioxopyrimidin-1(2H)-yl)phenoxy]naphthalene-1,4-diones were synthesized by the reaction of dihydro-1-(3-hydroxy- and 4-hydroxyphenyl)pyrimidine-2,4(1H,3H)-diones and their 5- and 6-methyl derivatives with 2,3-dichloro-1,4-naphthoquinone. Their stability in alkaline and acidic media was investigated. Four of the compounds exhibited good antimicrobial activity against Staphylococcus aureus, Mycobacterium luteum, Candida tenuis, and Aspergillus niger.     

3-(2-吡啶-3-乙烯基)-1H-吲哚钌配合物的合成及抗肿瘤性能

以3-(2-吡啶-3-乙烯基)-1H-吲哚(Indole)为配体与二联吡啶钌前体Ru(bPy)2Cl2进行配位反应,得到一种新型联吡啶钌配合物Ru-Indole,并通过1H NMR、ESI-MS及元素分析对配体及配合物进行了表征.研究结果表明,配合物具有良好的脂溶性,使得药物能够顺利地进入细胞内,克服了钌类配合物脂溶性...     

Preparation and chemistry of stable azidoiodinanes: 1-Azido-3,3-bis(trifluoromethyl)-3-(1H)-1,2-benziodoxol and 1-Azido-1,2-benziodoxol-3-(1H)-one

Azidoiodinanes 2,4,6 can be prepared from benziodoxols 1,3 and trimethylsilyl azide in the form of stable, crystalline compounds. These compounds are potentially useful reagents for electrophilic azidonation of organic substrates. For example, reaction of azide 6 with cyclohexene affords 2-azidocyclohexanone 7 in moderate yield.     

Synthesis and Dynamic NMR Study of a Functionalized Sulfonamide Phosphonate Diester

Abstract

Protonation of the highly reactive 1:1 intermediate produced in the reaction between triphenylphosphite and activated acetylene by sulfonamide leads to a phosphonate ylide, which undergoes methanol elimination in the presence of moisture to produce a highly functionalized sulfonamide phosphonate diester. A dynamic nuclear magnetic resonance (NMR) effect is observed in the ¹H NMR spectra of this compound as a result of restricted rotation around the single C?N bond. The coalescence temperature was observed at T_C = 352.5 K, and the free energy of activation (ΔG^#) for this process is 75.6 ± 2 kJ.mol^?1.

GRAPHICAL ABSTRACT     

Ionic liquid promoted synthesis of 3-(2′-benzothiazolo)-2,3-dihydroquinazolin-4(1H)-ones

3-(2′-Benzothiazolo)-2,3-dihydroquinazolin-4(1H)-ones have been synthesized in high yields in the presence of 1-butyl-3-methylimidazolium bromide [bmim]Br as an ionic liquid; the reaction work-up is simple and the ionic liquid can be easily separated from the product and reused.     

Synthesis and spatial structure of 4-(2-hydroxyethyl)-5-(2-hydroxyphenyl)-2H-1,2,4-triazolo-3(4H)-thione

By reaction of 2-vinyloxyethyl isothiocyanate with salicylic acid hydrazide a synthesis of the corresponding thiosemicarbazide was performed. Alkaline hydrolysis of the latter led to an intramolecular heterocyclization into 1,2,4-triazole derivative. When cyclization was carried out in the water-alkali medium, 2-vinyloxyethyl fragment was shown to be hydrolyzed to form 4-(2-hydroxyethyl)-5-(2-hydroxyphenyl)-2H-1,2,4-triazolo-3(4H)-thione, whose spatial structure was established by XRD analysis.     

Five-membered 2,3-dioxo heterocycles: LXIX. Direct heterocyclization of [3,4-dihydroisoquinolin-1(2H)-ylidene]-acetamides with 5-arylfuran-2,3-diones. Crystalline and molecular structure of (3E,5Z)-3-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-5-(2-oxo-2-phenylethylidene)pyrrolidine-2,4-dione

5-Arylfuran-2,3-diones react with (Z)-2-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]acetamides to give (3E,5Z)-5-(2-aryl-2-oxoethylidene)-3-[3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-pyrrolidine-2,4-diones. The crystalline and molecular structures of one of the products were determined by X-ray analysis.